JP6465316B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing urethane (meth) acrylate, and belongs to the technical field of active energy ray-curable composition and paint / coating.

  Conventionally, for various substrates such as metal, glass and plastic, a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design. The forming method is used. In particular, the plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, it is required that the surface of the plastic substrate is coated with a coating composition and is subjected to a so-called hard coat treatment to impart scratch resistance and improve surface hardness.

  Conventionally, as a method for improving the surface hardness of a plastic substrate, an active energy ray-curable composition comprising (meth) acrylate having an alicyclic skeleton excellent in hardness of a cured film is known (Patent Document 1 and the same). 2).

  On the other hand, as a coating agent having little stress during curing and good adhesion and curl resistance, a coating agent utilizing photocationic polymerization of cyclic ether is known (Patent Document 3). It is disclosed in the Examples that this method has better adhesion and curl resistance than a coating agent using photoradical polymerization of (meth) acrylate.

  A method of combining 4- (meth) acryloylmorpholine and a trifunctional or higher functional (meth) acrylate having one or more hydroxyl groups is known as a coating agent that is not easily affected by humidity and has good adhesion (Patent Document 4). ). Good adhesion is obtained by using 4- (meth) acryloylmorpholine.

JP 2003-268263 A JP 2013-49802 A JP 2007-284613 A JP 2012-111943 A

(Meth) acrylates having an alicyclic skeleton have a high glass transition point (Tg) and good hardness in many cases, but there is a tendency that adhesion to a substrate is difficult to obtain due to a large stress during active energy ray curing. is there. Moreover, in patent document 1 and the same patent document 2, the adhesiveness with respect to a plastic base material is not disclosed in the Example.
In the method described in Patent Document 2, a reactive polymer is produced in advance using a thermal polymerization initiator. If the thermal polymerization initiator used at this time remains, an active energy ray-curable composition is used. May be cured by polymerization during storage, and cannot be said to have sufficient stability.
In the method described in Patent Document 3, it is known that in the cationic polymerization, humidity under a working atmosphere greatly affects the curability. In particular, since hard coating is often applied as a thin film, the influence of humidity is likely to occur, and the desired curability and performance as a coating may not be obtained in the rainy season or summer.
In the method described in Patent Document 4, the shrinkage at the time of curing is large and the curl resistance cannot be improved.

  The present inventors have intensively studied to find a curable composition having a cured film excellent in hardness, adhesion and flexibility, and having better curl resistance. In addition, the inventors of the present invention have produced a urethane (meth) acrylate-containing reaction product that has excellent storage stability without producing turbidity even when produced without using an organic solvent. In order to find out the manufacturing method of the thing, earnest examination was performed.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the reason why the storage stability is reduced is the low molecular weight compound contained in the urethane (meth) acrylate-containing reaction product. It has been found that in order to reduce the molecular weight compound, this can be prevented by setting the hydroxyl value in the (meth) acrylic acid adduct of the starting aliphatic polyhydric alcohol compound to a specific value. In addition, the curable composition containing the urethane (meth) acrylate-containing reaction product has flexibility that the cured film is excellent in hardness, adhesion and followability to deformation of the substrate, and has curl resistance. As a result, the present invention was completed.
Hereinafter, the present invention will be described in detail.

  According to the curable composition of the present invention, since it is excellent in storage stability that does not generate turbidity during storage, it has good handling properties when used as a blending raw material for paints, coatings, and the like, and is further obtained. The cured film has high hardness and excellent adhesion, flexibility and curl resistance.

The present invention is a (meth) acrylic acid adduct of pentaerythritol, which is a mixture containing at least tetra (meth) acrylate of pentaerythritol and tri (meth) acrylate of pentaerythritol, and has a hydroxyl value of 180 to 300 mgKOH / Urethane (meth) acrylate-containing reaction product obtained by reacting compound (a1) [hereinafter referred to as “compound (a1)”] with a polyvalent isocyanate compound (a2) [hereinafter referred to as “compound (a2)”] The present invention relates to a curable composition containing the product (A).
Moreover, this invention relates also to the manufacturing method of the urethane (meth) acrylate containing reaction product which heats and mixes a compound (a1) and a compound (a2).

As a result of studying a curable composition excellent in hardness, adhesion, flexibility, and curl resistance of a cured film, the present inventors have found that a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound is used. Activity containing a urethane (meth) acrylate-containing reaction product obtained by reacting a polyvalent isocyanate compound with a compound having a hydroxyl value of 140 mgKOH / g or more, and a compound having an ethylenically unsaturated group at a specific ratio An energy ray curable composition was found (Japanese Patent Application No. 2013-151502).
However, it has been found by the inventors' subsequent examination that they have the following problems.
First, the raw material urethane (meth) acrylate-containing reaction product is preferably produced without using an organic solvent in an object or application in which it is preferable that the raw material does not contain an organic solvent or contains a small amount. That is, the organic solvent is not contained or the composition does not require a drying step, or the composition containing a small amount of the organic solvent can simplify the drying step. In addition, a composition containing no or a small amount of an organic solvent can be suitably used in applications requiring thick coating. In addition, a composition that does not contain an organic solvent contains a compound having a single (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) as a component of the composition. ) There is no problem that the acrylate volatilizes.
However, it has been found that a urethane (meth) acrylate-containing reaction product produced without using an organic solvent has a problem that turbidity occurs when stored for a long period of time.
Furthermore, it has been found that the performance is insufficient in applications where higher curl resistance is required.

As a result of detailed investigations by the present inventors, the above-described curable composition of the present invention has excellent storage stability such that turbidity does not occur during storage. It has been found that when it is used as a raw material, it has good handling properties, and the resulting cured film has high hardness and excellent adhesion, flexibility and curl resistance.
Hereinafter, the component (A) which is an essential component, other components, usage methods and the like will be described.

1. Component (A) The component (A) is a urethane (meth) acrylate-containing reaction product obtained by reacting the compound (a1) and the compound (a2).
The weight average molecular weight (hereinafter also referred to as “Mw”) of the component (A) is preferably 800 to 100,000, more preferably 1,000 to 10,000, and 1,200 to 5 Is more preferably 1,500, and particularly preferably 1,500 to 3,000.
Mw in the present invention means a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”).
Hereinafter, the manufacturing method of a compound (a1), a compound (a2), and (A) component is demonstrated.

1-1. Compound (a1)
The compound (a1) is a (meth) acrylic acid adduct of pentaerythritol and has a hydroxyl value of 180 to 300 mgKOH / g.
The hydroxyl value of the compound (a1) is from 180 to 300 mgKOH / g, preferably from 190 to 290 mgKOH / g, and more preferably from 200 to 280 mgKOH / g.
When the hydroxyl value of the compound (a1) is less than 180 mgKOH / g, the storage stability of the obtained component (A) is lowered, and the cured film of the resulting composition has hardness and adhesion to the substrate. Therefore, the followability to the deformation of the base material and the curl resistance are insufficient. On the other hand, when the hydroxyl value of the compound (a1) exceeds 300 gKOH / g, the molecular weight of the urethane (meth) acrylate in the component (A) obtained by the urethanization reaction becomes too high, and surface smoothness is obtained when it is used as a coating agent. It becomes worse or becomes incompatible with other components.
In addition, the hydroxyl value employ | adopts the value measured according to the method defined in JISK0070-1992.

The compound (a1) is preferably a compound obtained by an esterification reaction of pentaerythritol and (meth) acrylic acid.
(Meth) acrylic acid used in the reaction may be either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid, but only acrylic acid should be used. Is preferred.
In addition, in the production of the compound (a1), instead of (meth) acrylic acid, (meth) acrylic acid equivalent, (meth) acrylic acid halide, (meth) acrylic anhydride, (meth) acrylic acid are used. Esters may be used.

When the compound (a1) is produced by an esterification reaction of pentaerythritol and (meth) acrylic acid, the proportion of (meth) acrylic acid used is such that the hydroxyl value of the resulting (meth) acrylic acid ester is 180 to 300 mgKOH. There is no particular limitation as long as the amount is / g.
The molar amount of (meth) acrylic acid used is preferably less than the molar amount of the hydroxyl group of pentaerythritol to be used, preferably 0.75 to 1.25 molar equivalents relative to the total number of hydroxyl groups of pentaerythritol, More preferably, it is 0.85-1.15 molar equivalent.

Compound (a1) includes pentaerythritol tetra (meth) acrylate having no hydroxyl group (hereinafter referred to as “PETet”) and pentaerythritol tri (meth) acrylate having one hydroxyl group (hereinafter referred to as “PETri”). It is preferable to contain at least PETet, PETri, and more preferably at least dipentaerythritol di (meth) acrylate (hereinafter referred to as “PEDi”) having two hydroxyl groups.
The proportion of PETet and PETri in the compound (a1) is preferably 50% by weight or more, more preferably 65% by weight or more, and still more preferably 80% by weight or less as the total amount of PETet and PETri.
Furthermore, the ratio of PETet, PETri and PEDi in the compound (a1) is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 93% by weight or more as the total amount of PETet, PETri and PEDi. .

There is no restriction | limiting in particular as a manufacturing method of a compound (a1), Although well-known esterification reaction can be used, It is preferable to use a catalyst and a stabilizer.
As the catalyst, an acid catalyst can be preferably exemplified. Moreover, as a stabilizer, well-known polymerization inhibitors, such as hydroquinone monomethyl ether, can be mentioned suitably. It is also preferable to use oxygen as a stabilizer, particularly a polymerization inhibitor. For example, unnecessary polymerization of (meth) acrylic acid or (meth) acrylate can be prevented by producing the compound (a1) in an oxygen-containing atmosphere. Moreover, it is preferable that it is 1-20 volume%, and, as for the content rate of oxygen in atmosphere, it is more preferable that it is 1-10 volume%.
Moreover, it is preferable that the manufacturing method of a compound (a1) includes the method of refine | purifying at least by liquid-liquid extraction (separation). In the above embodiment, a compound having a hydroxyl value of 180 to 300 mgKOH / g can be easily produced.

1-2. Compound (a2)
The compound (a2) is a polyvalent isocyanate compound.
Various compounds can be used as the compound (a2).
Further, the compound (a2) is preferably a divalent isocyanate compound, and is preferably an aliphatic polyvalent isocyanate compound.
Specific examples of the preferred compound (a2) include aliphatic divalent isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and norbornane diisocyanate, and 2,4-tolylene diisocyanate and naphthalene diisocyanate. Aromatic divalent isocyanates such as xylene diisocyanate and diphenylmethane diisocyanate, and nurate trimers of these compounds.
Moreover, although a compound (a2) may be used individually by 1 type or may use 2 or more types together, it is preferable to use it individually by 1 type.

1-3. (A) Component Production Method Component (A) is produced by urethanization of the hydroxyl group in compound (a1) and the isocyanate group in compound (a2).

  (A) At the time of manufacture of a component, the reaction ratio (molar ratio) of the hydroxyl group in compound (a1) and the isocyanate group of compound (a2) is hydroxyl group: isocyanate group = 1: 0.6-1: 1. Is preferably 3, hydroxyl group: isocyanate group = 1: 0.8 to 1: 1.2, more preferably hydroxyl group: isocyanate group = 1: 0.9 to 1: 1. . The hardness of the obtained cured film is more excellent as it is the said aspect.

There is no restriction | limiting in particular as a manufacturing method of (A) component, A well-known method can be used.
For example, the compound (a1) and the compound (a2) may be heated and stirred. According to the production method, the obtained component (A) can be excellent in storage stability.

The addition reaction between the hydroxyl group and the isocyanate group can be performed without a catalyst, but a urethanization catalyst may be added in order to advance the reaction efficiently.
Examples of urethanization catalysts include organotin compounds such as dibutyltin dilaurate; acetylacetonate metal complexes such as iron acetylacetonate, zinc acetylacetonate and ruthenium acetylacetonate; metal organic weak acid salts such as lead naphthenate and potassium acetate And triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5; A tertiary amine compound such as diazabicyclo [4.3.0] nonene-5; and a trialkylphosphine compound such as triethylphosphine.
The proportion of the urethanization catalyst may be appropriately set according to the compound (a1), the compound (a2) and the catalyst to be used, but is preferably 0.01 to 1,000 wtppm with respect to the reaction solution, more preferably. Is 0.1 to 1,000 wtppm.

  What is necessary is just to set suitably as reaction temperature according to the kind and ratio, etc. of a compound (a1), a compound (a2), and a catalyst to be used, 60-130 degreeC is preferable, More preferably, it is 70-90 degreeC.

When the molecular weight of the component (A) produced by the reaction is increased, the reaction mixture becomes highly viscous and stirring may be difficult. Therefore, a reaction solvent can be blended in the reaction component.
The reaction solvent is preferably one that does not participate in the urethanization reaction, and examples thereof include aromatic compounds such as toluene and xylene, and organic solvents such as dimethylformamide.
The amount of the organic solvent to be used may be appropriately set according to the viscosity of the component (A), but is preferably set to be 0 to 70% by weight in the reaction solution.
Here, the reaction solution means the total amount of the raw material compound when only the raw material compound is used, and means the total amount including these when the reaction solvent or the like is used in addition to the raw material compound. Specifically, it is used to mean a solution in which the compound (a1), the compound (a2) and a reaction solvent used as necessary are combined.

In the urethanization reaction, a small amount of a chain extender can be blended for the purpose of adjusting the molecular weight.
As the chain extender, those usually used in a urethanization reaction can be used.
Specific examples of the chain extender include low molecular weight polyols, polyether polyols, polycarbonate polyols and polyester polyols.
Examples of the low molecular weight polyol include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane, and the like. Examples include polyols such as alkylene oxide adducts.
Examples of the polyether polyol include polyalkylene glycol having 3 or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polycarbonate polyol include a reaction product of carbonate and diol. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the diol include the low molecular weight polyol described above.
Examples of the polyester polyol include a reaction product of an acid component with at least one selected from the group consisting of the low molecular weight polyol, the polyether polyol, and the polycarbonate polyol. Examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof. Moreover, the ring-opening reaction product of polycarbonate diol and caprolactone is also mentioned.
The proportion of the chain extender used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the total component (A) finally obtained.

  Further, when the isocyanate group remains, the component (A) does not have an isocyanate group or a small amount of the isocyanate group is preferable from the viewpoint of hardness and stability. A compound having two or more (meth) acryloyl groups (hereinafter also referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) may be added.

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, which are (meth) acrylates derived from a trihydric or higher polyhydric alcohol, having two or more (meth) acryloyl groups, It is preferable that it is (meth) acrylate which has 1 or more.
Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, di (meth) acrylate of trimethylolpropane alkylene oxide adduct, di- or tri (meth) acrylate of pentaerythritol, penta Di or tri (meth) acrylate of alkylene oxide adduct of erythritol, di or tri (meth) acrylate of ditrimethylolpropane, di or tri (meth) acrylate of alkylene oxide adduct of ditrimethylolpropane, dipentaerythritol di, Di, tri, tetra or penta (meth) acrylate and isocyanurate alkylene oxide of tri, tetra or penta (meth) acrylate, dipentaerythritol alkylene oxide adduct Di (meth) acrylate of adduct, dipentaerythritol di, tri, tetra, penta, hexa, or hepta (meth) acrylate, alkylene oxide adduct of tripentaerythritol di, tri, tetra, penta, hexa, or hepta Examples include di (meth) acrylates of alkylene oxide adducts of (meth) acrylate and isocyanurate.
In this case, examples of the alkylene oxide include ethylene oxide and propylene oxide.
Among them, trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of ditrimethylolpropane and di, tri, tetra or penta (meth) acrylate of dipentaerythritol Preferably mentioned.

Component (A) is a urethane (meth) acrylate-containing reaction product, and PETri [tri (meth) acrylate of pentaerythritol] having one hydroxyl group contained in compound (a1) and PEDi [ In addition to urethane (meth) acrylate obtained by reacting a hydroxyl group such as di (meth) acrylate of pentaerythritol and an isocyanate group of compound (a2), PETet [pentaerythritol tetra (meth) acrylate] contained in compound (a1) is included. It is a mixture.
The component (A) preferably contains at least urethane (meth) acrylate and PETet, and contains at least urethane (meth) acrylate obtained by reacting PETri having one hydroxyl group with the compound (a2) and PETet. Is more preferable, urethane (meth) acrylate obtained by reacting PEDi having two hydroxyl groups, PETri having one hydroxyl group and compound (a2), and urethane (meta) having reacted with PETri having one hydroxyl group and compound (a2). It is further preferable that at least acrylate and PETet are included.
The component (A) is preferably a mixture of urethane (meth) acrylate and PETet.
The ratio of urethane (meth) acrylate and PETet may be appropriately set according to the purpose, but is preferably included at a weight ratio of urethane (meth) acrylate: PETet = 80: 20 to 92: 8. More preferably, it is contained in a weight ratio of (meth) acrylate: PETet = 75: 25 to 90:10. The hardness and adhesiveness of the cured film obtained are more excellent in the above range.

Further, as the component (A), a compound having a molecular weight distribution of 1,000 or less in a molecular weight distribution measured by GPC of 20 area% or less is excellent in storage stability and has other ethylenically unsaturated groups This is preferable because the compatibility of the cured film is good and the adhesion of the resulting cured film to the substrate is good. This ratio is more preferably 5 to 18 area%.
Furthermore, as the component (A), a component having a molecular weight of 500 or less in the molecular weight distribution measured by GPC is 18 area% or less because it has excellent storage stability and can impart flexibility to the cured film. preferable. This ratio is more preferably 10 to 13 area%.
The molecular weight distribution measured by GPC in the present invention means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: within the range of 25-50 ° C-Eluent: Tetrahydrofuran (hereinafter referred to as "THF")

The viscosity of the component (A) may be appropriately set according to the purpose. When no organic solvent is contained, the viscosity is preferably 8,000 to 600,000 mPa · s, more preferably 8,000 to 400,000 mPa · s. .
In the present invention, the viscosity of the component (A) when no organic solvent is contained means a value measured at 50 ° C. using an E-type viscometer.
In addition, when the component (A) is produced in the presence of an organic solvent, the viscosity of the organic solvent solution of the component (A) may be appropriately set according to the purpose and depends on the concentration of the component (A). However, the value measured at 25 ° C. using an E-type viscometer is preferably 10 to 600,000 mPa · s.

2. Curable composition The present invention relates to a curable composition containing the component (A) as an essential component.
As a manufacturing method of a composition, what is necessary is just to follow a conventional method, for example, it can manufacture by stirring and mixing (A) component and another component as needed.
In this case, heating can be performed as necessary. What is necessary is just to set suitably as a heating temperature according to the component which the composition to be used contains, the base material which coats a composition, the intended purpose, etc., but 30 to 80 degreeC is preferable.

The viscosity of the composition may be appropriately set according to the purpose, and is preferably 200 to 600,000 mPa · s for both the solvent-free composition containing no organic solvent and the solvent-type composition containing the organic solvent. More preferably, it is 200 to 400,000 mPa · s.
When the composition of the present invention is used for coating applications, the above-mentioned viscosity range is preferable. However, in the case of a coating agent that further requires a low viscosity, a value measured at 25 ° C. using an E-type viscometer, 200 to 3,000 mPa · s is preferable.

The cured product of the composition of the present invention is excellent in hardness, flexibility and curl resistance.
Specifically, the hardness is such that the pencil hardness of a cured film having a thickness of 1 to 30 μm formed on a plastic film having a thickness of 100 μm is H or more. Moreover, as a softness | flexibility, there exists an effect that the crack and peeling of a cured film are not seen in the core rod of diameter 5mm in a mandrel bending test. Furthermore, the curl resistance has the effect that when the 100 μm thick plastic film on which a cured film with a thickness of 1 to 30 μm is cut is cut into 10 cm × 10 cm, the raised heights of the four corners are 8 mm or less. It is what you play.

The composition of the present invention can be used as an active energy ray-curable composition and a thermosetting composition, and can be preferably used as an active energy ray-curable composition.

The composition of the present invention contains the component (A) as an essential component, but various components can be blended depending on the purpose.
Preferable examples of other components include compounds having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as “component (B)”], photopolymerization initiator [hereinafter referred to as “(C)”. Component ”], thermal polymerization initiator [hereinafter referred to as“ component (D) ”], organic solvent [hereinafter referred to as“ component (E) ”] and the like.
Hereinafter, these components will be described.

2-1. (B) component (B) component is a compound which has an ethylenically unsaturated group other than (A) component, and mix | blends in order to provide various physical properties to the hardened | cured material of a composition.
Examples of the ethylenically unsaturated group in component (B) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, with a (meth) acryloyl group being preferred.
In the following, “monofunctional” means a compound having one ethylenically unsaturated group, “X function” means a compound having X ethylenically unsaturated groups, and “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.

  In the component (B), specific examples of the monofunctional ethylenically unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxy phthalate Ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2- Ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meta) of alkylphenol alkylene oxide adduct (meta Of alkylene oxide adduct of acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, paracumylphenol (Meth) acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned.

  Specific examples of the bifunctional (meth) acrylate compound include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tetramethylene glycol. Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol F alkylene oxide adduct, butanediol di (meth) Examples include acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. In addition, epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.

As the trifunctional or higher functional (meth) acrylate compound, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and tris (2- (meth) acryloyloxyethyl) isocyanurate.
In addition to this, a polyfunctional urethane (meth) acrylate other than the component (A) obtained by urethanizing a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate, a polyfunctional epoxy (meth) acrylate having a novolak skeleton And polyfunctional polyester (meth) acrylate.

(B) As a component, it is preferable that a polyfunctional ethylenically unsaturated compound is included from a viewpoint of the hardness of the cured film obtained, and it is more preferable that a polyfunctional (meth) acrylate compound is included.
The component (B) preferably contains an ethylenically unsaturated compound having a hydroxyl group from the viewpoint of adhesion of the resulting cured film to the substrate and curl resistance, and a (meth) acrylate compound having a hydroxyl group It is more preferable that a monofunctional (meth) acrylate compound having a hydroxyl group is more preferable.
Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Are preferable, and 4-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate are particularly preferable.
The component (B) is preferably a monofunctional ethylenically unsaturated compound and / or a bifunctional ethylenically unsaturated compound.

(B) A component may contain individually by 1 type, or may contain 2 or more types.
As a content rate of (B) component, 3-60 weight part is preferable with respect to 100 weight part of total amounts of (A) component and (B) component, and it is more preferable that it is 4-45 weight part. It is especially preferable that it is -30 weight part. Within the above range, the cured film obtained is more excellent in curling resistance and hardness.

2-2. (C) Component When the composition of the present invention is used as an active energy ray curable composition and further used as an electron beam curable composition, the component (C) (photopolymerization initiator) is not contained, and the electron It can also be cured by a wire.
When using the composition of this invention as an active energy ray hardening-type composition, it is preferable to further contain (C) component from a viewpoint of the ease of hardening or cost.
As the component (C) in the present invention, various known photopolymerization initiators can be used.
The component (C) is preferably a radical photopolymerization initiator.

  Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl Acetophenone compounds such as 2-methylpropan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyldiphenylsulfide; methylbenzoyl Α-ketoester compounds such as formate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid; 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Phosphine oxide compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2- Acetophenone / benzophenone hybrid photoinitiators such as methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2- And oxime ester photopolymerization initiators such as octanedione; and camphorquinone.

  Among these, acetophenone compounds, benzophenone compounds, and phosphine oxide compounds are preferable, and acetophenone compounds are particularly preferable.

As the component (C), only one type may be used, or two or more types may be used in combination.
The content ratio of component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. Particularly preferred is ˜5 parts by weight. Within the above range, the composition has excellent curability and the resulting cured film has excellent scratch resistance.
In addition, a sclerosing | hardenable component is a component hardened | cured with a heat | fever or an active energy ray, means (A) component, and when mix | blending (B) component mentioned above, (A) component and (B) component are included. means.

2-3. (D) When using a thermal-polymerization initiator composition as a thermosetting composition, a thermal-polymerization initiator can be mix | blended.
The composition of this invention can mix | blend a thermal-polymerization initiator and can also be heat-hardened.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide , P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

The amount of these thermal polymerization initiators used is preferably not more than 10 parts by weight with respect to 100 parts by weight of the total amount of curable components.
When the thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of normal radical thermal polymerization. In some cases, the thermal polymerization initiator is used in combination with a photopolymerization initiator and photocured for the purpose of further improving the reaction rate. Curing can also be performed.

2-4. (E) Organic solvent The composition of the present invention preferably further contains (E) an organic solvent from the viewpoints of applicability and handleability of the composition.
Various known organic solvents can be used as the organic solvent in the present invention.
(E) As a component, what melt | dissolves (A) component is preferable, and when (B) component is contained, what melt | dissolves (A) component and (B) component is more preferable.

Preferred specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, Aromatic compounds such as toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Is mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

As the component (E), only one type may be used, or two or more types may be used in combination.
(E) It is preferable that the content rate of a component is 10-1,000 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, It is more preferable that it is 50-500 weight part, 50-300 More preferably, it is part by weight. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

2-5. Other components The composition of this invention may further contain other components other than (A) component-(E) component.
As other components, known additives can be used. For example, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane coupling agents, surface modifiers, polymers, acids Examples include generators, pigments, dyes, tackifiers, polymerization inhibitors, and the like.
Other components described later may be used alone or in combination of two or more.

<Ultraviolet absorber>
Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine ultraviolet absorbers; 2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- ( Benzotriazole ultraviolet absorbers such as (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole; benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, ethyl-2-cyano -3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl Cyanoacrylate ultraviolet absorbers such as acrylate, titanium oxide particles, zinc oxide particles, and inorganic particles, and the like to absorb the ultraviolet rays or the like tin oxide particles.

Among the compounds, benzotriazole ultraviolet absorbers are particularly preferable.
The content ratio of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1-2 parts by weight.

<Light stabilizer>
As the light stabilizer, a known light stabilizer can be used. Among them, a hindered amine light stabilizer (HALS) is preferably exemplified.
Specific examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, and the like.
Examples of commercially available hindered amine light stabilizers include BASIN, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100.

  The content ratio of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1-1 weight part.

<Acid substance>
Although the composition of this invention is excellent in the adhesive material to base materials, such as a plastics, adhesiveness can be improved further by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, and the like.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluenesulfonic acid is particularly preferable.
The content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, with respect to 100 parts by weight of the total amount of the curable component, More preferably, it is -0.5 weight part. Within the above range, the adhesion to the substrate is excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Inorganic particles>
As the inorganic particles, metal oxide particles are preferable.
The metal oxide particles are preferably metal oxide particles or composite metal oxide particles made of one or more metals selected from the group consisting of silicon, zirconium, titanium, antimony, tin, cerium, aluminum, zinc and indium. Can be mentioned.

The average particle diameter of the inorganic particles may be selected according to the use, but is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and particularly preferably 10 to 100 nm. Within the above range, the transparency and appearance of the cured film are good.
In the present invention, the average particle diameter of the inorganic particles means a particle diameter when assuming that the particles are true spherical particles from the specific surface area of the sample obtained by the BET method.

The inorganic particles may be surface-modified particles.
As the surface modifier, a known one can be used, and a silane coupling agent, a titanium coupling agent, and the like are preferable.
Among these, a silane coupling agent is more preferable, and a compound having an ethylenically unsaturated group and an alkoxysilyl group is particularly preferable. It is excellent in the hardness and curl resistance of the cured film obtained as it is the said aspect. Specific examples of the silane coupling agent include the same compounds as those described below.
Further, the amount of surface modification of the inorganic particles is not particularly limited, but the ratio of the surface modifier to the inorganic particles is 1.0 to 45.0% by weight based on the total weight of the surface modifier and the inorganic particles. It is preferable to have made it react with.

  The content ratio of the inorganic particles is preferably 25 to 400 parts by weight, more preferably 30 to 200 parts by weight, and 50 to 150 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably. It is excellent in transparency, adhesiveness, abrasion resistance, and curl resistance of the cured film obtained as it is the said aspect.

<Antioxidant>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
As a phenolic antioxidant, hindered phenols, such as di-t-butylhydroxytoluene, can be mentioned preferably, for example. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Preferable examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

  The content of the antioxidant is preferably 0.01 to 5 parts by weight and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable components. In the above embodiment, the composition is excellent in stability, and curability and adhesive strength are good.

<Silane coupling agent>
The composition of the present invention may further contain a silane coupling agent for the purpose of improving the adhesion to the substrate.
The silane coupling agent used in the present invention is not particularly limited, and a known silane coupling agent can be used.
Preferable specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, 3-mercaptopropyl Chill dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.
Moreover, the compound which has the ethylenically unsaturated group and alkoxysilyl group which were mentioned above can also be used.

  The content of the silane coupling agent is preferably 0.1 to 10 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable components. It is excellent in adhesiveness with a base material as it is the said range.

<Surface modifier>
In the composition of the present invention, a surface modifier may be added for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
In addition, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a coating film as it is the said range.

<Polymer>
The composition of the present invention may further contain a polymer other than the component (A) for the purpose of further improving the curl resistance of the resulting cured film.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
It is preferable that the content rate of a polymer is 0.01-10 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the curl resistance of the cured film obtained as it is the said range.

3. Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, the composition can be cured by irradiation with active energy rays or by heating to obtain a cured product.
Specifically, in the case of an application such as a coating agent and an adhesive, the composition is applied to a substrate to be applied by a normal coating method, and then in the case of an active energy ray-curable composition, an active energy ray. In the case of a thermosetting composition, a method of heating and curing may be used. In the case of applications such as molding materials, the composition is injected into a predetermined mold and then cured in the case of an active energy ray curable composition by irradiation with active energy rays, or a thermosetting composition. In the case of a thing, the method of heating and hardening etc. is mentioned.
A general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
In addition, (C) component (photopolymerization initiator) and (D) component (thermal polymerization initiator) are used in combination with the composition, irradiated with active energy rays, and then heat-cured, thereby adhering to the substrate. A method for improving the property can also be adopted.

The substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
Specific examples of plastics include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of the wood include natural wood and synthetic wood.
Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of inorganic materials include glass, mortar, concrete, and stone.
Among these, a plastic substrate is particularly preferable.

  The method of applying the composition of the present invention to the substrate may be appropriately set depending on the purpose, and is a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma. Examples of the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, and a micro gravure coater.

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the use of the base material to be used or the base material having the manufactured cured film, but is preferably 1 to 100 μm, more preferably 5 to 40 μm. .

  When the composition is an active energy ray curable composition and contains an organic solvent, the composition is heated and dried to evaporate the organic solvent. The drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation.

Examples of the active energy rays for curing the composition of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are particularly preferable. Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 200 to 2,000 mJ / cm ² is more preferable.

4). Applications The composition of the present invention can be used for various applications, preferably as an active energy ray-curable composition, and specifically, coating agents such as paints, inks, nanoimprints, and lens sheets. Examples include resins, resin films, and adhesives.

A cured product obtained by curing the active energy ray-curable composition of the present invention, particularly a cured film, is excellent in hardness, adhesion to a substrate, followability to deformation of the substrate, and curl resistance. It can be preferably used as a coating agent. Furthermore, as the coating agent, a so-called hard coat coating agent based on a plastic can be preferably used.
For example, the display panel front plate, building material use, lighting equipment, mobile phone, smartphone, tablet terminal display and housing, home appliance housing, various lenses such as glasses.
Specific examples of the front plate for the display board include an electric bulletin board, a display, a signboard, an advertisement, and a sign.
Examples of using wood as a base material include woodwork products such as stairs, floors and furniture. Examples of using metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.

The resin film produced from the composition of the present invention can be preferably used particularly as an optical film.
The optical film formed from the composition of the present invention can be used for various optical applications. More specifically, a film used for a liquid crystal display device such as a polarizer protective film for a polarizing plate, a support film for a prism sheet, and a light guide film, and a touch panel integrated liquid crystal display device, various functional films (for example, hard coat) Films, decorative films, transparent conductive films) and surface films (for example, moth-eye type antireflection films and films with a texture structure for solar cells), light resistance for outdoor use such as solar cells (weather resistance) ) Applications such as films, films for LED lighting / organic EL lighting, and transparent heat-resistant films for flexible electronics.
Furthermore, as a transparent conductive film, in a cover-integrated touch panel in which a touch sensor such as ITO is directly formed on the cover glass of the touch panel, plastic is used as the cover material instead of glass, and the touch sensor such as ITO is directly applied to the plastic. It can also be used for so-called OPS (One Plastic Solution).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, unless otherwise specified, “part” means part by weight and “%” means percent by weight.

1. Production example
1) Raw material production example 1 [ Production of compound (a1)]
Since nitrogen gas containing 5% by volume of oxygen was not blown into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a blower, 301 parts (4.18 mol) of acrylic acid, pentaerythritol [Kouei Chemical Co., Ltd. ) Made. Hereinafter, it is referred to as “PE”. 167 parts (1.23 mol), 7 parts of sulfuric acid, 0.14 part of hydroquinone monomethyl ether (hereinafter referred to as “MEHQ”) and 224 parts of toluene were mixed, and the reaction temperature was about 80 ° C. and the conditions were 370 Torr (absolute pressure). The reaction was continued until 45 mol% of all hydroxyl groups in the PE had been esterified while removing the condensed water.
The generated condensed water was 28 parts, and 42 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
A 20% aqueous sodium hydroxide solution corresponding to a molar amount of 1 times the molar amount of the reaction solution to which toluene was added was added with stirring to carry out a neutralization treatment to remove excess acrylic acid and sulfuric acid. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off toluene.
The obtained acrylate was 185 parts, and the hydroxyl value was 204 mgKOH / g.

2) Raw material production example 2 [ Production of compound (a1)]
Condensed water was used under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 moles) of acrylic acid, 167 parts (1.23 moles) of PE, 7 parts of sulfuric acid, 0.14 parts of MEHQ and 224 parts of toluene were used. While removing, the reaction was continued until 30% of all hydroxyl groups in the PET were esterified.
The generated condensed water was 18 parts, and 83.5 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
By the same operation as in Raw Material Production Example 1, the same amount of sodium hydroxide aqueous solution and water were used for neutralization treatment and water washing treatment, and then toluene was distilled off.
The obtained acrylate was 120 parts, and the hydroxyl value was 224 mgKOH / g.

3) Raw material production example 3 [ Production of compound (a1)]
Condensation under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 moles) of acrylic acid, 167 parts (1.23 moles) of PE, 7 parts of sulfuric acid, 0.14 parts of MEHQ and 224 parts of toluene are used. While removing water, the reaction was continued until 15% of all hydroxyl groups in the PET were esterified.
The generated condensed water was 10 parts, and 101 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
By the same operation as in Raw Material Production Example 1, the same amount of sodium hydroxide aqueous solution and water were used for neutralization treatment and water washing treatment, and then toluene was distilled off.
The obtained acrylate was 50 parts, and the hydroxyl value was 240 mgKOH / g.

4) Raw material production example 4 [ Production of compound (a1)]
Since 5% by volume oxygen-containing nitrogen gas was not blown into the same flask as in Production Example 1, 1163 parts (16.2 moles) of acrylic acid, 732 parts (5.4 moles) of PE, and p-toluenesulfonic acid (29 parts) Then, cupric chloride (4 parts) was mixed, and all the water in PE was removed without removing condensed water under the conditions of reaction temperature of about 90 ° C., external temperature of 102 ° C., internal / external temperature difference ΔT 12 ° C., and 101 kPa (absolute pressure). The reaction was continued until 48% of the hydroxyl groups were esterified.
After completion of the reaction, the reaction mixture was cooled and a 20% aqueous sodium hydroxide solution (32 parts) was added to the reaction solution to neutralize the strong acid catalyst.
Put the reaction liquid (1,959 parts) into a separatory funnel, then add cyclohexane (600 parts), methyl ethyl ketone (2,400 parts), and further water (1,250 parts), mix, and leave the liquid to stand. Separation was performed and the lower layer was extracted to separate the organic phase. Next, an equimolar amount of 20% aqueous sodium hydroxide solution (840 parts) was added with stirring to the acid content of the organic phase to carry out neutralization treatment. The organic phase was separated and washed with water. After washing with water, the organic phase was again separated and heated under reduced pressure to distill off the solvent.
The obtained acrylate was 874 parts, and the hydroxyl value was 280 mgKOH / g.

5) Comparative raw material production example 1 [Production of acrylate other than compound (a1)]
Condensation under the same conditions as in Raw Material Production Example 1 except that 1,000 parts of acrylic acid (13.89 moles), 555 parts of PE (4.08 moles), 23 parts of sulfuric acid, 0.4 parts of MEHQ and 744 parts of toluene are used. While removing water, the reaction was continued until 63% of all hydroxyl groups in the PET were esterified.
The generated condensed water was 185 parts. After completion of the reaction, 690 parts of toluene was added.
The same amount of water as in Raw Material Production Example 1 was used, except that a 20 wt% aqueous sodium hydroxide solution corresponding to 1.1 times the molar amount of the acid content of the reaction liquid added with toluene was used. After performing neutralization treatment and water washing treatment in the same manner as in Production Example 1, toluene was distilled off.
The obtained acrylate was 865 parts, and the hydroxyl value was 163 mgKOH / g.

6) Production Example 1 [Production of component (A)]
100 parts of the compound (a1) (hydroxyl value: 204 mgKOH / g) obtained in Raw Material Production Example 1 in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and 5 vol% oxygen-containing nitrogen gas inlet , 2,6-di-tert-butylcresol (hereinafter referred to as “DBC”) 0.07 part and dibutyltin dilaurate (hereinafter referred to as “DBTL”) 0.07 part, and at 70 ° C. hexamethylene diisocyanate (hereinafter referred to as “DBC”). 29 parts ("HDI") was added dropwise in about 1 hour, reacted at 80 ° C for 6 hours, and IR (infrared absorption) analysis of the reaction product confirmed that the residual isocyanate group was 0.25% or less. The reaction was terminated.
The obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-1)”) had a molecular weight obtained by GPC measurement under the following conditions, and the polystyrene-converted Mw was 2,026, and the viscosity at 50 ° C. was 13, It was 800 mPa · s. Components having a molecular weight of 1000 or less obtained by GPC measurement under the following conditions were 16 area%, and components having a molecular weight of 500 or less were 14 area%.
○ GPC measurement conditions / apparatus: GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Shodex KFG (8 μm 4.6 × 10 mm) manufactured by Showa Denko KK, two types of this column Watergel HR 4E THF (7.8 × 300 mm) + styragel HR 1THF (7.8 × 300 mm)
Column temperature: 40 ° C
Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate of 0.75 mL / min. In addition, in Production Examples 2 to 4 and Comparative Production Examples 1 and 2 under the same conditions GPC measurement was performed.

7) Production Example 2 [Production of Component (A)]
A urethanization reaction was carried out in the same manner as in Production Example 1 except that 100 parts of the compound (a1) (hydroxyl value: 224 mgKOH / g) obtained in Raw Material Production Example 2 was used and 32 parts of HDI was appropriately adjusted.
Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-2)”) was 2,330, and the viscosity at 50 ° C. was 23,300 mPa · s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 14 area%, and components having a molecular weight of 500 or less were 13 area%.

8) Production Example 3 [Production of Component (A)]
The urethanization reaction was carried out in the same manner as in Production Example 1 except that 100 parts of the compound (a1) (hydroxyl value: 240 mgKOH / g) obtained in Raw Material Production Example 3 was used and 35 parts of HDI was appropriately adjusted.
Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-3)”) was 3,630, and the viscosity at 50 ° C. was 45,300 mPa · s. The component having a molecular weight of 1,000 or less obtained by GPC measurement was 13 area%, and the component having a molecular weight of 500 or less was 11 area%.

9) Production Example 4 [Production of Component (A)]
Same as Production Example 1 except that 100 parts of the compound (a1) (hydroxyl value: 224 mgKOH / g) obtained in Raw Material Production Example 2 was used and 42 parts of isophorone diisocyanate (hereinafter referred to as “IPDI”) was appropriately reduced. The urethanization reaction was performed.
Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-4)”) was 2,290, and the viscosity at 50 ° C. was 350,000 mPa · s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 14 area%, and components having a molecular weight of 500 or less were 13 area%.

10) Production Example 5 [Production of Component (A)]
In a flask similar to Production Example 1, 100 parts of the compound (a) (hydroxyl value: 280 mgKOH / g) obtained in Raw Material Production Example 4, 0.07 parts of DBC, 0.07 parts of DBTL, and acetic acid as a solvent. 90 g of ethyl (hereinafter referred to as “EtOA”) was charged, 40 parts of HDI was added dropwise at 55 ° C. in about 1 hour, and reacted at 75 ° C. for 6 hours to confirm that the residual isocyanate group was 0.25% or less. The reaction was completed after confirmation.
Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-5)”) is 3,825, and the viscosity at 25 ° C. of an EtOA solution containing 61% by weight of (UA-5) is 168 mPa・ It was s. Components having a molecular weight of 1000 or less obtained by GPC measurement were 7.5 area%, and components having a molecular weight of 500 or less were area 6.9%. This value is a value excluding the solvent EtOA.

11) Production Example 6 [Production of Component (A)]
In the same flask as in Production Example 1, HDI trimer as a compound (a2) [trade name: Duranate TPA-100, manufactured by Asahi Kasei Corporation]. Hereinafter, 29.7 parts of "TPA"), 0.04 part of DBC, 0.04 part of DBTL, and 50 parts of methyl ethyl ketone (hereinafter referred to as "MEK") were charged and obtained in Raw Material Production Example 1 at 65 ° C. A solution obtained by diluting 50 parts of the obtained compound (a1) (hydroxyl value: 204 mgKOH / g) with 50 parts of MEK was added dropwise over about 1 hour. The reaction was carried out at 75 ° C. for 2 hours, and the reaction was completed after confirming that the residual isocyanate group was 0.25% or less by IR (infrared absorption) analysis of the reaction product.
Mw of the obtained urethane acrylate-containing reaction product [hereinafter referred to as “(UA-6)”] was 51,000, and the viscosity at 25 ° C. of the MEK solution containing 44% of (UA-6) was 57 mPa · s. s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 16 area%, and components having a molecular weight of 500 or less were 14 area%.

12) Comparative Production Example 1 [ Production of urethane acrylate other than component (A)]
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, a mixture of pentaerythritol triacrylate (PETri) and pentaerythritol tetraacrylate (PETet) [Aronix M-305 manufactured by Toagosei Co., Ltd .: hydroxyl value 100 mg KOH / g. Hereinafter, it is also referred to as “M-305”. ] 159.2 g (containing 0.3 mol of PETri and 0.2 mol of PETet), 0.092 g of 2,6-di-tert-butyl-4-methylphenol and 0.055 g of DBTL were charged, and the liquid temperature was 70 ° C. While stirring at ˜75 ° C., 25.2 g (0.15 mol) of HDI was added dropwise. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours, and the reaction was terminated by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. The urethane acrylate-containing reaction product [hereinafter, "(UA'-1)") was obtained.
The Mw of (UA′-1) was 1,350, and the viscosity at 25 ° C. was 29,900 mPa · s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 32 area%, and components having a molecular weight of 500 or less were 26 area%.

13) Comparative production example 2 [ Production of urethane acrylate other than component (A)]
A urethanization reaction was carried out in the same manner as in Production Example 1 except that 100 parts of an acrylate of pentaerythritol having a hydroxyl value of 163 mg KOH / g obtained in Comparative Raw Material Production Example 1 was used and 23 parts of HDI was appropriately adjusted.
Mw of the obtained urethane acrylate-containing reaction product [hereinafter referred to as “(UA′-2)”] was 1,650, and the viscosity at 50 ° C. was 5,500 mPa · s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 18 area%, and components having a molecular weight of 500 or less were 16 area%.

14) Comparative Production Example 3 [ Production of urethane acrylate other than component (A)]
In Production Example 6, the reaction was carried out in the same manner as in Production Example 6 except that instead of the compound (a1), a solution obtained by diluting 50 parts of M-305 with 50 parts of MEK was used.
Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA′-3)”) is 3,400, and the viscosity at 25 ° C. of the MEK solution containing 40% of (UA′-3) is 4 mPa · s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 33 area%, and components having a molecular weight of 500 or less were 27 area%.

In Production Examples 1 to 6 and Comparative Production Examples 1 to 3, the physical properties of the raw material compounds used and the obtained urethane acrylate-containing reaction products are summarized in Tables 1 and 2.
The storage stability was evaluated by the following method.
In a 100 ml screw can, 60 g of urethane acrylate reaction product was placed and allowed to stand at room temperature. The lid was periodically opened, and the time course of the reaction product was visually observed to confirm the presence or absence of precipitates.

2. Examples and Comparative Examples
1) Preparation of composition According to Tables 3 and 4 described later, for 100 parts of component (A) and urethane acrylate other than component (A) obtained above (hereinafter referred to as “component (A) ′”). , (C) component (photopolymerization initiator) 1-hydroxycyclohexyl phenyl ketone [Irgacure 184 manufactured by BASF Japan Ltd.] Hereinafter, it is referred to as “Irg184”. ] And the component (E) (organic solvent) for adjusting the viscosity were stirred and mixed so as to have the ratios shown in Tables 3 and 4 to obtain an active energy ray-curable composition.

The resulting composition was applied to a polyethylene terephthalate film A-4300 (film thickness: 100 μm, hereinafter referred to as “PET film”) manufactured by Toyobo Co., Ltd. using a bar coater # 8 so that the film thickness after drying was 5 μm. And dried for 3 minutes in a dryer at 100 ° C.
After drying, using a high-pressure mercury lamp equipped with a conveyor (H06-L41 manufactured by Eye Graphics Co., Ltd., lamp output 80 W / cm), UV-A illuminance 450 mW / cm ² and irradiation energy 200 mJ / cm ² . Was irradiated.
The obtained cured film was used and evaluated according to the following method. The results are shown in Tables 3 and 4.

3. Evaluation method
1) Pencil hardness About the obtained cured film, pencil hardness was measured by 750g load according to JISK5600-5-4.

2) Adhesiveness The obtained cured film was cut with 1 mm vertical and horizontal intervals with a cutter knife to form 100 squares of 1 mm × 1 mm size, and Nichiban Co., Ltd. # 405 made by Nichiban Co., Ltd. After cellophane tape was applied, it was peeled off strongly. The following three levels were evaluated based on the number of remaining films after peeling.
◎: The number of remaining film cells is 90 or more ○: The number of remaining film cells is 80 to 89 ×: The number of remaining film cells is 79 or less

3) Scratch resistance About the obtained cured film, steel wool # 0000 was used, the surface of the cured film after reciprocating 100 times with 5 kg load was visually observed, the presence or absence of scratches was confirmed, and the following three levels were evaluated. did.
◎: No scratch, ○: Less than 5 scratches, ×: More than 5 scratches

4) The cured film formed on the curl-resistant PET film was cut into 100 mm × 100 mm, the heights at which the four corners were lifted were measured, and the average value was obtained. A smaller value indicates better curl resistance.

5) Flexibility (flexibility)
According to a mandrel test (JIS K5600-5-1), a PET film having a cured film formed around a core rod having a diameter of 3 mm to 10 mm was wound, and the minimum diameter at which the cured film was not cracked or peeled was evaluated.

  In addition, the numerical value described in the lower part of each component column of Table 3 and 4 represents content (unit: weight part) in a composition.

4). Evaluation results As is clear from the results of Examples 1 to 6, the composition of the present invention is excellent in hardness, adhesion, scratch resistance, curl resistance and flexibility, and maintains a good surface hardness. However, it had both flexibility.
On the other hand, the compositions of Comparative Examples 1 to 3 are compositions containing urethane acrylate produced from a raw material having a hydroxyl value of less than 180 mgKOH / g, and the compositions of Comparative Examples 1 and 2 have hardness In addition, the composition of Comparative Example 3 is excellent in hardness, adhesion, scratch resistance, and flexibility, but is inferior in curling resistance, although it is excellent in scratch resistance. Hardness and flexibility were not compatible.

  The composition of the present invention can be used for various uses such as a coating agent, ink, shaping resin, resin film and adhesive, preferably as an active energy ray hardening composition, and the resulting cured film has a surface hardness. , Since it can achieve both adhesion and flexibility, it can be preferably used as a coating agent composition.

Claims (13)

A (meth) acrylic acid adduct of pentaerythritol, a mixture containing at least tetra (meth) acrylate of pentaerythritol and tri (meth) acrylate of pentaerythritol, having a hydroxyl value of 180 to 300 mgKOH / g A curable composition comprising a urethane (meth) acrylate-containing reaction product (A) obtained by reacting (a1) with a polyvalent isocyanate compound (a2). The curable composition according to claim 1, wherein the compound (a1) has a hydroxyl value of 200 to 290 mgKOH / g.   The curable composition according to claim 1 or 2, wherein the compound (a2) is an aliphatic polyvalent isocyanate.   The component (A) includes any one of components having a molecular weight of 1,000 or less in a molecular weight distribution measured by gel permeation chromatography (hereinafter referred to as “GPC”) of 20 area% or less. The curable composition according to item.   The curable composition according to any one of claims 1 to 4, wherein the component (A) contains 18 area% or less of a component having a molecular weight of 500 or less in a molecular weight distribution measured by GPC.   The compound (a1) comprises pentaerythritol tetra (meth) acrylate having no hydroxyl group, pentaerythritol tri (meth) acrylate having one hydroxyl group, and di (meth) acrylate of pentaerythritol having two hydroxyl groups. The curable composition according to any one of claims 1 to 5, comprising at least.   The active energy ray hardening-type composition containing the composition of any one of Claims 1-6.   Furthermore, the active energy ray hardening-type composition of Claim 7 containing a photoinitiator.   The active energy ray hardening-type coating agent composition containing the composition of any one of Claims 1-6.   Furthermore, the active energy ray hardening-type coating agent composition of Claim 9 containing a photoinitiator.   The active energy ray-curable coating composition according to claim 9 or 10, which is used for plastic coating. A (meth) acrylic acid adduct of pentaerythritol, a mixture containing at least tetra (meth) acrylate of pentaerythritol and tri (meth) acrylate of pentaerythritol, having a hydroxyl value of 180 to 300 mgKOH / g The manufacturing method of the urethane (meth) acrylate containing reaction product which heat-mixes (a1) and a polyvalent isocyanate compound (a2), without using an organic solvent. The method for producing a urethane (meth) acrylate-containing reaction product according to claim 12, wherein the compound (a1) has a hydroxyl value of 200 to 290 mgKOH / g.